Thiazolylphenyl phosphates



United States Patent 3,518,279 THIAZOLYLPHENYL PHOSPHATES BernardMiller, Princeton, N.J., assiguor to American Cyanamid Company,Stamford, Conn., a corporation of Maine No Drawing. Filed Aug. 29, 1967,Ser. No. 663,971 Int. Cl. C07d 91/32 US. Cl. 260-302 8 Claims ABSTRACTOF THE DISCLOSURE Pesticidal compounds of the formula:

wherein Q is X is either oxygen or sulfur, Y is lower alkyl, loweralkoxy, lower alkylthio, halo-substituted lower alkyl, halo-substitutedlower alkoxy, phenyl or lower alkylamino and each Y may be the same ordifferent, Z is hydrogen, lower alkyl or halo, R is hydrogen, loweralkyl or phenyl, and R stands for hydrogen, lower alkyl, cyano,carb(lower)alkoxy or acetyl are disclosed, They may be prepared from thehydroxy thiazole compounds having the above formula wherein Q is H.

The present invention relates to novel phenylthiazoles and method forpreparing the same. More particularly, it relates to compounds of thestructure:

wherein Q is X is either oxygen or sulfur, Y is lower alkyl, lower 1alkoxy, lower alkylthio, halo-substituted lower alkyl, halo-substitutedlower alkoxy, phenyl or lower alkylamino and each Y may be the same ordiflerent, Z is hydrogen, lower alkyl or halo, R is hydrogen, loweralkyl or phenyl, and R stands for hydrogen, lower alkyl, cyano,carb(lower)alkoxy or acetyl.

In general, the compounds of the present invention may be synthesizedconveniently by the initial preparation of an appropriatehydroxyphenylthiazole and, thereafter, effecting reaction between thelatter and a phosphoruscontaining compound, such as an0,0-dialkylphosphorohalothioate, 0,0-dialkylphosphorohaloate, O-alkylalkanephosphonohalothioate, O-alkyl N monoalkylphosphoroamidohaloate,O-alkyl-N,N-dialkylphosphoroamidohalothiate, N,N'dialkylphosphorodiamidohalothiate, O-alkyl phenylphosphonohalothiate,0,0-diphenylphosphorohaloate, or the like.

The over-all reaction may be graphically written as:

Z 0 Ha hydroxythiobenzamide haloaldehyde or haloketone HHa lL R1 S Zhydrohalide salt oia hydroxyphenylthiazole wherein R, R- and Z are thesame as hereinabove defined and Ha IS a halogen atom, such as chloro,bromo or iodo.

HHa R R 'N OH base N CH II ll s s Z Z Rl R1 [III] N OH 1;? l Ha'P(Y)2 -aR Z hydroxyphenylthiazole phosphorylating agent thiazolephenylphosphatederivative The hydroxythiobenzamides employed in Reaction I aboveinclude illustratively:

p-Hydroxythiobenzamide, 3-chloro-4-hydroxythiobenzamide,m-Hydroxythiobenzamide, o-Hydroxythiobenzamide,3-hydroxy-5-ethylthiobenzamide, 2-chloro-4-hydroxythiobenzamide, and2-hydroxy-S-bromothiobenzarnide.

An equivalent amount of the latter is reacted with a haloaldehyde orhaloketone, usually at temperatures between 0 C. and C.

Exemplary haloaldehydes or haloketones employed in Reaction I are:chloroacetone, bromoacetone, 2-ch1oroacetaldehyde, l-phenyl 2chloroacetaldehyde, methyl ester of a-chloroacetoacetic acid, ethylester of a-chloroacetoacetic acid, 3-aceto-3-chloroacetone, 3-aceto-3-bromoacetone, ethyl ester of a-chloro-a-methylacetoacetic acid,2-methyl-2-chloroacetaldehyde, and 3-chloro- 3-cyanoacetone.

It is a good practice to carry out the process illustrated by Reaction Iin the presence of a suitable solvent, such as ether, benzene, toluene,methyl alcohol or ethyl alcohol.

It has been found that the illustrated reactions above can be carriedout in sequence without separation of the several reaction products, orthey may be conducted stepwise. Advantageously, the reaction of ReactionII is carried out in the presence of an acid acceptor which may be aninorganic or organic base, and usually in the presence of a suitablesolvent, such as water, ethyl alcohol, n-propyl alcohol, t-butylalcohol, ethyl acetate, butyl acetate, methyl isobutyl ketone, methylethyl ketone, ethylene glycol, dimethyl ether and benzene. Contemplatedbases are, for example, sodium hydroxide, potassium hydroxide, sodiumcarbonate, triethyl amine, potassium butoxide and sodium acetate. Basesufiicient to neutralize the hydrohalide salt of thehydroxyphenylthiazole and the acid formed during reaction is providedfor optimum results. Illustrative of the latter compounds prior toneutralization are:

2-p-hydroxyphenyl-4-methylthiazole hydrochloride,

2p-hydroxyphenyl-4-methyl-5-carbethoxythiazole hydrobromide,

2-p-hydroxyphenylthiazole hydrochloride,

2-m-hydroxyphenylthiazole hydrochloride,

2-ohydroxyphenyl-4-methylthiazole hydrochloride,

2- [3 -hydroxy-5-ethyl] pheny1-4-methyl-5 -carb ethoxythiazolehydrochloride,

2- [2-chloro-4-hydroxy 1 phenyl-4,5-methylthiazole hydrochloride,

2- [2-hydroxy-5-bromo] phenyl-4-methyl-5-acetylthiazole hydrochloride,

2-m-hydroxyphenyl-4-ethyl-S-carbethoxythiazole hydrochloride,

2-p-hydroxyphenyl-S-methylthiazole hydrochloride,

2-p-hydroxypheny1-5-cyano-4methylthiazole hydrochloride, and

2-p-hydroxyphenyl-4 phenylthiazole hydrochloride.

These compounds find utility as intermediates in the preparation ofinsecticidal thiazolylphenyl phosphates.

In general, there may be employed as phosphorohaloate reactants employedin Reaction III above the following:

0,0-dimethylphosphorochloridothioate, 0,0-diethylphosphorochloridothioate,

O-methyl, O-ethyl phosphorochloridothioate, 0,0-di-iso-propylphosphorobromidothioate, 0,0-di-n-butyl phosphorochloridothioate,0,0-di-sec-pentyl phosphorochloridothioate, 0,0-dimethylphosphorochloridate,

0,0-diethyl phosphorochloridate,

O-ethyl ethyl phosphonochloridothioate, O-ethyl-N,N-dimethylphosphoramidochloridothioate, O-ethyl, phenylphosphonochloridothioate,O-ethyl-N-isopropyl phosphoramidochloridothioate, O-ethyl-N-methylphosphoramidochloridothioate, Diethylphosphorochloridotrithioate, andDiethylphosphinothioyl bromide.

Typical thiazolephenyl phosphates or thiophosphates r 0 are, forinstance:

4 Di-ethylthio-m- (4-ethyl-5-carbethoxy-2-thiazolyl) phenyl phosphate,Bis-chloromethyl-p-(4-methyl-2-thiazolyl)phenyl phosphate,Di-phenyl-p-(5-methyl-2-thiazolyl)phenyl phosphate,0,0-dimethyl-O-p-(5-cyano-4-methyl-2-thiazolyl)phenyl phosphorothioate,and 0,0-dimethyl-O-p-(4-phenyl-2-thiazolyl)phenyl phosphorothioate Thethiazolylphenyl phosphates or thiophosphates of the present inventionfind utility as insecticides, acaricides and as nematocides.

To facilitate a further understanding of the present invention, thefollowing illustrative examples are presented. These are not to be takenas limitative of the invention. Unless otherwise stated, the parts areby weight and the analyses are in percent.

EXAMPLE 1 Preparation of 2-p-hydroxyphenyl-4-methylthiazolehydrochloride Chloroacetone (3.05 parts) is added to a solution ofp-hydroxythiobenzamide (5.0 parts) in ethyl alcohol. The solution isrefluxed for 2.5 hours, then cooled in ice and filtered to give 3.8parts of golden yellow solid, melting point 248 C.-252 C. The motherliquors are evaporated to one third their volume to give an additional1.3 parts of product. The product is recrystallized from ethyl alcoholto give material melting at 249 C.253 C.

Analysis-Calcd. for NOSClC H (percent): C, 52.8; H, 4.39; N, 6.16; S,13.4; C1, 15.6. Found (percent): C, 53.4; H, 4.30; N, 5.85; S, 12.9; C1,14.5.

EXAMPLE 2 Preparation of 2-p-hydroxyphenyl-4-methyl-5-carbethoxythiazole hydrobromide The same procedure is followed as inExample 1 except the chloroacetone is replaced with the ethyl ester ofa-bromo acetoacetic acid (CH COCHBrCO C H resulting in a 59% yield ofproduct which is recrystallized from methanol to give a yellow solid,melting point of 207 C.-209' C.

Analysis.Calcd for NSO C H Br (percent): C, 45.4; H, 4.07; N, 4.07; S,9.30. Found (percent): C, 43.42; H, 4.13; N, 4.13; S, 10.01.

EXAMPLE 3 Preparation of 2-p-hydroxyphenylthiazole hydrochloride Thesame procedure is followed as in Example 1 except the chloroacetone isreplaced by chloroacetaldehyde yielding the desired product which, whenrecrystallized from a methanol-acetone solution, has a melting. point ofC.-192 C.

Analysis.Calcd for C H SNOCI (percent): C, 50.7; H, 3.78; N, 6.58; S,15.02; Cl, 16.62. Found (percent): C, 50.43; H, 4.08; N, 6.71; S, 15.00;C1, 16.48.

EXAMPLE 4 Preparation of 0,0-diethy1-O-p-(4-methyl-2-thiazolyl)- phenylphosphorothioate 3.0 parts of 2-p-hydroxyphenyl-4-methylthiazolehydrochloride are added to a solution of 2.95 parts of potassiumt-butoxide in t-butylalcohol. The mixture is stirred for 20 minutes;then heated on a steam bath until a homogeneous solution is obtained.2.50 parts of 0,0-diethylphosphorochloridothioate are added and themixture stirred at room temperature for 16 hours. Water is then added tothe solution, which is extracted with methylene chloride. The methylenechloride layer is evaporated to give 4.1 parts of yellow oil, n =l.58l5.The nuc ear magnetic resonance and infrared spectra of the product arein agreement with the assigned structure.

Analysis.--Calcd for NPS O C H (percent): C,

48.5; H, 5.31; N, 4.13; S, 18.9; P, 9.16. Found (percent): C, 48.90; H,5.33; N, 4.16; S, 18.60; P, 8.95.

EXAMPLE P Preparation of 0,0-dimethyl-O-p-(4-rnethyl-2-thiazolyl)phenylphosphorothioate The same procedure is followed as inExample 4 except that 0,0-diethylphosphorochloridothioate is replaced by0,0-dimethylphospliorocloridothioate. The product has an 115 16002.

1 'kinalysis.Calcd for PNS O C H (percent): C, 45.7;.H, 4.44; N, 4.44;S, 20.3; P, 9.84. Found (percent): C, 45.75; H, 4.46; N, 4.39; S, 20.38;P, 9.91.

EXAMPLE 6 Preparation bf 0,0-diethyl-O-p-(4-methyl-2 thiazoly1)- phenylphosphate The procedure is followed as in Example 4 in every detailexcept that 0,0-diethylphosphorochloridothioate is replaced by0,0-diethylphosphorochloridate. The product' has an n 1.5495.

Analysis-Calcd for NPSO C H (percent): C, 51.4; H, 5.50; N, 4.28; P,9.48; S, 9.78. Found (percent):

C, 48.12; H, 4.60; N, 4.26; P, 9.41; S, 9.54.

EXAMPLE 7 Preparation of 0,0-diethyl-O-p-(2-thiazolyl)phenylphosphorothioate The procedure is followed as in Example 4 in every.detail except that the 2-p-hydroxyphenyl-4-methylthia- .zolehydrochloride is replaced by 2-p-hydroxyphenyl-4- thiazolehydrochloride. The producthas an n =1.5732.

' Analysis.-Calcd for C H PNS O (percent): C, 4.75; H, 4.90; N, 4.26; S,19.48; P, 9.41. Found (percent): C, 46.61; H, 4.86; N, 3.95; S, 18.66;P, 9.18.

EXAMPLE 8 Preparation of 0,0-diethyl-O-p-(2-thiazolyl)phenylphosphorothioate Repeating Example 5 in every detail except that the2-p-hydroxyphenyl-4-methylthiazole hydrochloride is replaced by2-p-hydroxyphenyl-4-thiazole hydrochloride.

The product has an ru 1.6057.

Analysis.-Calcd for C H PNS O (percent): C, 43.9; H, 4.02; N, 4.66; S,21.25; P, 10.2. Found (percent): C, 43.47; H, 4.41; N, 4.83; S, 21.96;P, 10.63.

EXAMPLE 9 Preparation of 0,0-diethyl-O-p-(4-methyl-5-carbethoxy-2-thiazolyl)phenyl phosphorothioate The procedure is followed as inExample 4 except the Z-p-hydroxyphenyl-4-methylthiazole hydrochloride isreplaced by 2 p hydroxyphenyl-4-methyl-5-carbethoxythiazolehydrobromide. The product has an n =1.5685.

Analysis.-Calcd for PNS O C H (percent): C, 49.2; H, 5.30; N, 3.38; S,15.4; P, 7.47. Found (percent): C, 49.20; H, 5.39; N, 3.39; S, 15.53; P,7.49.

EXAMPLE 10 Preparation of0,0-dimethyl-O-p-(4-rnethyl-5-carbethoxy-2-thiazolyl)phenylphosphorothioate EXAMPLE 11 A variety of thiazolylphenylphophorothioates and phosphoroates are prepared by the procedure ofExample 10 as by reacting an appropriately substituted bydroxyphenylthiazole hydrohalide with the appropriate phosphorochloridothioateor phosphorochloridate as follows:

(A) Z-m-hydroxyphenyl-thiazole hydrochloride anddimethylphosphorochloridothioate to yield 0,0-dirnethylO-m-2-thiazolyl)phenyl phosphorothioate;

(B) 2-o-hydroxyphenyl-4-methylthiazole hydrochloride anddiethylphosphorochloride to yield diethyl 0 (4-methyl-2-thiazolyl)phenyl phosphate;

(C) 2,3-hydroxy-5-ethylphenyl-4-methyl-S-carbethoxythiazolehydrochloride and dimethylphosphorochloridothioate to yield0,0-dimethyl-O-3-(4-methyl-5-carbethoxy-2-thiazolyl)-5-ethylphenylphosphorothioate;

(D) 2,2 chloro 4-hydroxyphenyl-4,S-methylthiazole hydrochloride anddiethylphosphonyl chloridate to yield diethyl-4-(4,5-methyl-2-thiazolyl)2 chlorophenyl phosphate;

(E) 2,2-hydroxy-5-bromophenyl-4-methyl-S-acetylthiazole hydrochlorideand dimethylphosphorochloridothioate to yield0,0-dimethylO-2-(4cyano-5-acetyl-2-thiazolyl)- S-brornophenylphosphorothioate;

(F) 2-p-hydroxyphenylthiazole hydrochloride anddidimethylaminophosphonylchloridothioate to yield didimethylaminoO-p-(2-thiazolyl)phenyl phosphorothioate;

(G) 2 m-hydroxyphenyl-4-ethyl-5-carbethoxythiazolehydrochloride anddi-ethylthiophosphonylchloridate to yield di-ethylthio-m 4 ethyl-5carbethoxy-Z-thiazolyl) phenyl phosphate;

(H) 2-p-hydroxyphenyl-4-methylthiazole hydrochloride anddi-chloromethylphosphonylchloridate to yield dichloromethyl-p-(4-methyl-2-thiazolyl phenyl phosphate;

(I) 2-p-hydroxyphenyl-S-methylthiazole hydrochloride anddi-phenylphosphonylchloridothioate to yielddiphenyl-p-(5-arnethyl-2-thiazolyl)phenyl phosphate;

(J) 2-p-hydroxyphenyl 5 cyano-4-methylthiazole hydrochloride anddimethylphosphorochloridothioate to yield 0,0dimethyl-0-p-(5-cyano-4-methyl-2-thiazolyl)- phenyl phosphorothioate;and

(K) 2-p-hydroxyphenyl-4-phenylthiazole hydrochloride anddimethylphosphorochloridothioate to yield0,0-dimethyl-O-p-(4-phenyl-2-thiazolyl)phenyl phosphorothioate.

Application of the phosphorylated derivatives synthesized from thecompounds of the invention for purposes of insecticide control can beaccomplished employing both conventional type formulations andequipment. The compounds may, for instance, be formulated as wettablepowders, dusts, dust concentrates, emulsifiable concentrates and thelike, which are amenable to application with conventional spraying ordusting apparatus.

Wettable powder formulations are generally prepared by admixing fromabout 25% to about 95%, by weight, of active ingredient with finelyground clay, such as kaolin or attapulgite, either with or without asurface active agent, emulsifier or spreader-sticker. The latter is thendispersed in Water for spray application.

.Dusts and dust concentrates are similarly prepared using from about 5%to about of active ingredient and from about to about 5% of finelydivided inert ingredients. These dusts are generally applied as such, orthey may be further diluted with finely ground inert solids and thenapplied with conventional dusting apparatus.

Emulsifiable concentrates may be prepared by dissolving or dispersingthe active ingredient in organic solvent, with or without emulsifyingagents, surfactants or the like. Such formulations are then diluted witheither Water or an appropriate organic diluent prior to application.

The insecticidal activity of the compounds of this invention uponvarious insect species is evaluated using the following methods:

(1) Bean aphidAphis fabae Scopoli: Compounds are tested as 0.1%solutions or suspensions in 65% acetone- 35% water. Two-inch fiber pots,each containing a nasturtium plant two inches high and infested withabout 150 aphids two days earlier, are placed on a turntable (4 rpm.)and sprayed for two revolutions with a No. 154 DeVilbiss Atomizer at 20p.s.i. air pressure. The spray tip is held about six inches from theplants and the spray is directed so as to give complete coverage of theaphids and the plants. The sprayed plants are laid on their sides onwhite enamel trays which have had the edges coated with No. 50 SAE oilas a barrier. Mortality estimates are made after holding for two days at70 F., and 50% RH. Compounds producing greater than 75% kill are furthertested at tenfold dilutions in 65% acetone-35% water.

(2) Southern armyworm-Prdenia eridania (Crarner): The solutions from theaphid test are also used for this one. Sieva lima bean primary leavesare dipped for three seconds in the test solution and set in a hood on ascreen to dry. When dry, each leaf is placed in a 4- inch petri dishwhich has a moist filter paper in the bottom and ten third-instararmyworm larvae about long. The dishes are covered and held at 80 F.,and 60% RH. After 2 days, mortality counts and estimates of the amountof feeding are made. Compounds showing partial kill and/or inhibition offeeding are held an extra day for further observations. Those materialswhich produce greater than 50% mortality or which inhibit feeding arefurther tested at ten-fold dilutions in 65% acetone-35% water.

(3) Two-spotted spider mite -Tetranychus urticae (Koch): Sieva lima beanplants with primary leaves three to four inches long are infested withabout 100 adult mites per leaf four hours before use in this test. Themite and egg infested plants are dipped for three seconds in a .01%solution prepared as in the above tests, and the plants set in the hoodto dry. They are held for two days at 80 F., 60% R.H., and the adultmite mortality estimated on one leaf under a stereoscopic microscope.The other leaf is left on the plant an additional five days and thenexamined at 10X power to estimate the kill of eggs and of newly-hatchednymphs, giving a measure. of ovicidal and residual action, respectively.

(4) Confused flour beetle Tribolium confusum Jacquelin duVal: Compoundsare formulated as 1% dusts by mixing 0.1 gram of the compound with 9.9grams of Pyrax ABB talc, wetting with 5 ml. of acetone and grinding witha mortar and pestle until dry. 125 mg. of this 1% dust is then blowninto the top of a dust settling tower with a short blast of air atp.s.i. The dustis-allow'ed to settle on four-inch petri dishes for twominutes, giving a deposit of approximately 87 mg./sq. foot (.094 'mg./sq. cm.) of the 1% dust. The dishes are removed and adult confused flourbeetles are added immediately. The dishes are held for three days at 80F. and R.H., following which mortality counts are made. 7

(5) Large milkweed bug0ncopeltus fasciatus Dallas: The 1% dustsdescribed above are used in this test. 25 mg. of the 1% dust issprinkled evenly over the glass bottom of a seven-inch diameter cage,using a screenbottom plastic cup about /s-inch in diameter as anapplicator, giving a deposit of approximately 94 mg./ sq. foot (.108mg./sq. cm.) of the 1% dust. Water is supplied in a two-ounce bottlewith a cotton wick, twenty adult bugs are added and a screen coverplaced on the top. Mortality counts are made after holding for threedays at 80 F. and 60% RH.

(6) Common malaria mosquito-Anoph8les quadrimaculatus Say Larvicidetest: Groups of 25 larvae of the common malaria mosquito are transferredwith a medicine dropper to a 50ml. beaker containing 25 ml. of water.The test compound is formulated as an emulsion containing 0.1 gram oftest material, 0.2 gram of Alrodyne 315 emulsifier, 10 ml. of acetoneand 90 ml. of water. This 1000 p.p.m. emulsion is diluted ten-fold withacetone-35% water to give 100 p.p.m. One milliliter of the 100 p.p. m.emulsion is pipetted into 225 m1. of water TABLE I.EFFICACY AGAINSTVARIOUS INSECT SPECIES, EXPRESSED AS PERCENT MORTALITY Southern Milk-Mos- Southern Aphids armywonn Spider Flour weed quito, House- 00m mite,beetle, bug, .4 fly, rootwonn, Structure .1% .01% .01% 1% p.p.m.50p.p.m. 50lb./acre CH i (C H Oh-lO- 90 0 0 0 66 0 100 100 50 CH (CH0);-P0- 100 90 O 0 100 0 100 100 100 011; t (C2H O)2lO 100 100 0 92 4824 100 50 S CH ll N ommi-P-o-W T 100 o o COzCzHs CH; t N (C H O)z-P--O-W 10 0 0 0 0 0 20 100 80 S\ s 002021 15 QMW (CzH50)z-P0-- 100 50 100 30100 100 100 100 100 100 o N (CH;0)z-i"0 T 100 99 100 30 37 100 15 100100 S- N (CzH O)zlO- H 100 50 100 96 82 100 O 100 65 in a 400 ml. beakerand stirred vigorously. The larvae in 25 ml. of water are added, givinga concentration of 0.4 ppm. Mortality counts are made after 24 hours at80 F.

(7) HouseflyMusca domestica Linnaeus: Groups of 25 adult femalehouseflies are lightly anesthetized with CO placed in wide-mouth pintmason jars, and covered with a screen cap. The test compound isformulated as an emulsion containing 0.1 gram of test material, 0.2 gramof Alrodyne 315 emulsifier, 10 ml. of acetone and 90 ml. of water. Twomilliliters of this emulsion are diluted to 40 ml. With 10% sugarsolution in a 10-gram glass vial, giving a concentration of 50 ppm. Themouth of the vial is covered with a single layer of cheesecloth,inverted and placed on the screen cap, so that the flies can feed on thesolution through the screen. Mortality counts are made after two days at80 F.

(8) Southern corn rootworm-Diabrotica undecimpunctata howardi Barber:The compound is formulated as a dust and incorporated into the soil atthe equivalent of 50 pounds per 6-inch acre. The soil is sub-sampledinto one-ounce wide mouth bottles, and ten 6- to 8-day old rootwormlarvae added to each bottle, which is then capped. Mortality counts aremade after six days at 80 F., 60% RH.

A summary of the data produced in the above tests is presented on thepreceding page in Table I for certain compounds of this invention.

I claim:

1. A compound of the formula:

10 wherein Q is X is either oxygen or sulfur, Y is lower alkyl, loweralkoxy, lower alkylthio, halo-substituted lower alkyl, halosubstitutedlower alkoxy, phenyl or lower alkylamino and each Y may be the same ordifferent, Z is hydrogen, lower alkyl or halo, R is hydrogen, loweralkyl or phenyl, and R stands for hydrogen, lower alkyl, cyano, carb(lower)- alkoxy or acetyl.

2. The compound according to claim 1: 0,0-diethyl-O p-(4-methyl-2-thiazo1yl)phenyl phosphorothioate.

3. The compound according to claim 1: 0,0-dimethyl- O-p-(4methyl-2-thiazolyl)phenyl phosphorothioate.

4. The compound according to claim 1: 0,0-diethyl-O-p-(4-methyl-2-thiazolyl)phenyl phosphate.

5. The compound according to claim 1: 0,0-diethyl-O- p- Z-thiazolyl)phenyl phosphorothioate.

6. The compound according to claim 1: 0,0-dimethyl- O-p-(2-thiazolyl)phenyl phosphorothioate.

7. The compound according to claim 1: 0,0-diethyl-O- p- (4-methyl-5-carbethoxy-2-thiazolyl phenyl phosphorothioate.

8. The compound according to claim 1: 0,0-dimethyl- O-p-(4-methyl-5carbethoxy 2-thiazolyl)phenyl phosphorothioate.

References Cited FOREIGN PATENTS 6,400,465 7/1964 Netherlands.

ALEX MAZEL, Primary Examiner R. J. GALLAGHER, Assistant Examiner US. Cl.X.R. 424200

